US4421910A - Polymer stabilization - Google Patents
Polymer stabilization Download PDFInfo
- Publication number
- US4421910A US4421910A US06/423,386 US42338682A US4421910A US 4421910 A US4421910 A US 4421910A US 42338682 A US42338682 A US 42338682A US 4421910 A US4421910 A US 4421910A
- Authority
- US
- United States
- Prior art keywords
- polymer
- poly
- metal salt
- zinc
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 230000006641 stabilisation Effects 0.000 title 1
- 238000011105 stabilization Methods 0.000 title 1
- -1 arylene sulfide Chemical compound 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- OFROEAZLQCMCPL-UHFFFAOYSA-L zinc;dicyclohexyl-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].C1CCCCC1P(=S)([S-])C1CCCCC1.C1CCCCC1P(=S)([S-])C1CCCCC1 OFROEAZLQCMCPL-UHFFFAOYSA-L 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000003860 storage Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- GKXZRMYDEMWOSP-UHFFFAOYSA-L cobalt(2+);dicyclohexyl-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Co+2].C1CCCCC1P(=S)([S-])C1CCCCC1.C1CCCCC1P(=S)([S-])C1CCCCC1 GKXZRMYDEMWOSP-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- PHKIJCYPUQXCNK-UHFFFAOYSA-L C(CCCCCCCCCCCCCCCCCCC)P([S-])(=S)CCCCCCCCCCCCCCCCCCCC.[Mn+2].C(CCCCCCCCCCCCCCCCCCC)P([S-])(=S)CCCCCCCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCCCC)P([S-])(=S)CCCCCCCCCCCCCCCCCCCC.[Mn+2].C(CCCCCCCCCCCCCCCCCCC)P([S-])(=S)CCCCCCCCCCCCCCCCCCCC PHKIJCYPUQXCNK-UHFFFAOYSA-L 0.000 description 1
- AEZQFZSIHDWTBH-UHFFFAOYSA-L C1(=CC=CC=C1)P([S-])(=S)C1=CC=CC=C1.[Cr+2].C1(=CC=CC=C1)P([S-])(=S)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P([S-])(=S)C1=CC=CC=C1.[Cr+2].C1(=CC=CC=C1)P([S-])(=S)C1=CC=CC=C1 AEZQFZSIHDWTBH-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- ZSQXMNYXCKBHLI-UHFFFAOYSA-L cobalt(2+);di(cyclooctyl)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Co+2].C1CCCCCCC1P(=S)([S-])C1CCCCCCC1.C1CCCCCCC1P(=S)([S-])C1CCCCCCC1 ZSQXMNYXCKBHLI-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MWJVQJKVXWGXEC-UHFFFAOYSA-L copper;butyl-(2-methylpropyl)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Cu+2].CCCCP([S-])(=S)CC(C)C.CCCCP([S-])(=S)CC(C)C MWJVQJKVXWGXEC-UHFFFAOYSA-L 0.000 description 1
- UYBAKFRLJRIRDF-UHFFFAOYSA-L copper;dimethyl-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Cu+2].CP(C)([S-])=S.CP(C)([S-])=S UYBAKFRLJRIRDF-UHFFFAOYSA-L 0.000 description 1
- KZDCCTWGFMXEGZ-UHFFFAOYSA-L dibenzyl-sulfanylidene-sulfido-$l^{5}-phosphane;nickel(2+) Chemical compound [Ni+2].C=1C=CC=CC=1CP(=S)([S-])CC1=CC=CC=C1.C=1C=CC=CC=1CP(=S)([S-])CC1=CC=CC=C1 KZDCCTWGFMXEGZ-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- AJYGICLQWBDHRN-UHFFFAOYSA-L zinc;di(cycloheptyl)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].C1CCCCCC1P(=S)([S-])C1CCCCCC1.C1CCCCCC1P(=S)([S-])C1CCCCCC1 AJYGICLQWBDHRN-UHFFFAOYSA-L 0.000 description 1
- ZXLANCRFLHEPFR-UHFFFAOYSA-L zinc;didodecyl-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCP([S-])(=S)CCCCCCCCCCCC.CCCCCCCCCCCCP([S-])(=S)CCCCCCCCCCCC ZXLANCRFLHEPFR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
Definitions
- This invention relates to improving the characteristics of arylene sulfide polymer compositions.
- this invention relates to the use of cure promoters in poly(arylene sulfide) polymer compositions.
- this invention relates to the use of cure promoters in poly(arylene sulfide) polymer compositions to enhance cross-linking or substantial alteration of physical properties during heating.
- this invention relates to the use of metal salts of dihydrocarbyldithiophosphinic acid as curing agents for arylene sulfide polymers, e.g., poly(phenylene sulfide), the resulting polymer products, and to a process for enhancing the cure of such polymers.
- arylene sulfide polymers In the production of arylene sulfide polymers, it is sometime desirable that the melt flow and molecular weight of the polymer be changed during processing of the polymer.
- Various procedures have been utilized to cause arylene sulfide polymers to change in physical properties during processing. It is well known that arylene sulfide polymers can be treated in a manner such that the polymer properties substantially change during heating of the polymer by incorporating into the polymer a curing promoter. A new group of curing agents has now been discovered.
- an object of this invention is to provide a process for promoting the curing of arylene sulfide polymers.
- a further object of this invention is to provide cured arylene sulfide polymers.
- Another object of this invention is to provide effective curing agents for poly(phenylene sulfide).
- the curing of arylene sulfide polymers is accelerated by the addition of a finite, but small effective amount of at least one metal salt of dihydrocarbyldithiophosphinic acid which promotes crosslinking of the polymer during heating.
- the curing of poly(phenylene sulfide) polymer during heating is promoted by the addition of a metal dihydrocarbyldithio phosphinate.
- an arylene sulfide polymer e.g., poly(phenylene sulfide) is heated in the pressure of a finite, but small effective amount, sufficient to enhance curing (based on the storage modulus results obtained with a Rheometric Dynamic Spectrometer) of the polymer of at least one metal dihydrocarbyldithiophosphinate, particularly cobalt and zinc dicyclohexyldithiophosphinates.
- Arylene sulfide polymers which can be employed in the process of this invention include arylene sulfide polymers which have a melt flow of at least about 10 and generally within the range of about 20 to about 400 and higher (determined by the method of ASTM D 1238-70, modified to a temperature of 316° C. and using a 5-kg weight, the value being expressed as g/10 min.).
- the arylene sulfide polymers can be linear, branched or lightly cross-linked.
- the preferred arylene sulfide polymer is a linear poly(p-phenylene sulfide) (PPS) having a melting or softening point of at least 150° C., preferably 230° C. to 330° C.
- PPS poly(p-phenylene sulfide)
- the method by which the polymers of this description are produced is not critical, preferably the polymer employed in the process is prepared by use of polyhaloaromatic compounds, alkali metal sulfides, and organic amides.
- the arylene sulfide polymers for use in this invention can be produced by the method of U.S. Pat. No. 3,354,129, which is hereby incorporated by reference.
- the polymer employed can be prepared by use of a p-dihalobenzene, an alkali metal sulfide, an organic amide, and an alkali metal carboxylate as in U.S. Pat. No. 3,919,177, optionally, together with an alkali metal hydroxide such as sodium hydroxide.
- an alkali metal hydroxide such as sodium hydroxide.
- the metal salts of dihydrocarbyldithiophosphinic acid used as curing promoters according to the invention have the general formula ##STR1## where M is a metal selected from among copper, zinc, chromium, manganese, cobalt and nickel, n is the valence of M and is generally 2, and R, R' are the same or different hydrocarbon (hydrocarbyl) radicals containing from 1 to about 20 carbon atoms, preferably from about 4 to about 12 carbon atoms, selected from among alkyl, cycloalkyl, aryl and combinations thereof such as alkaryl. Cycloalkyl radicals are presently preferred.
- Exemplary compounds include:
- nickel(II) dibenzyldithiophosphinate and the like and mixtures.
- Zinc and cobalt dicyclohexyldithiophosphinates are presently preferred.
- the amount of curing promoter incorporated into the arylene sulfide polymer will be a finite, effective amount sufficient to accelerate curing of the polymer.
- the curing agent additives of this invention are employed in an amount within the range of about 0.2 to about 5, preferably about 0.5 to 2 weight percent based on the weight of the arylene sulfide polymer.
- compositions can contain other ingredients conventionally employed in arylene sulfide polymer compositions.
- fillers such as titanium dioxide, calcium carbonate, aluminum oxide, aluminum silicate, ferric oxide, silicon dioxide, asbestos fibers, glass fibers, and poly(tetrafluoroethylene), pigments, resins, and/or plasticizers, and the like can be present.
- the cure promoter can be incorporated into the arylene sulfide polymer at any stage of processing, preferably prior to being subjected to elevated temperature.
- the cure promoters are incorporated into the arylene sulfide polymer, such as a poly(phenylene sulfide) polymer, prior to forming articles by injection molding.
- the processes of this invention of incorporating the cure promoters into the polymer can be conducted batch-wise or continuously.
- a series of samples was prepared by mixing individual portions of a linear poly(p-phenylene sulfide), abbreviated PPS, with a specified metal dihydrocarbyldithiophosphinate, when employed.
- PPS linear poly(p-phenylene sulfide), abbreviated PPS
- the PPS was produced in the manner described in U.S. Pat. No. 3,919,177.
- the recovered polymer was in the form of a powder (fluff) having a melt flow of 250 g/10 minutes as determined in accordance with ASTM D 1238-70, modified to a temperature of 316° C. and using a 5 kg weight.
- the PPS powder was admixed with about 50 mL of an acetone solution containing 0.15 g of the metal dihydrocarbyldithiophosphinate.
- the solvent was removed by evaporation over a suitable period of time at ambient conditions, e.g. overnight or longer, if needed, in a laboratory fume hood.
- the dried powders were stirred and additionally dried in a vacuum oven at room temperature (about 23° C.) for approximately 2 hours.
- Discs measuring 1 ⁇ 0.25 inches (2.54 ⁇ 0.64 cm) were compression molded from about 2.5 g of each mixture at room temperature by employing a mold and a laboratory press using a platen pressure of about 10,000 psig (69 MPa). Each cold molded disc was subsequently compression molded into test buttons measuring about 1 ⁇ 0.1875 inches (2.54 ⁇ 0.48 cm) at 325° C.
- the molding cycle typically comprised 21/2 minutes at a platen pressure of about 5,000-10,000 psig (34-69 MPa) and 21/2 minutes at a platen pressure of about 30,000 psig (207 MPa). While maintaining the latter pressure, heating was discontinued and cooling started by circulating tap water through the platens. When the mold temperature reached about 121° C., the pressure was released and the test button was removed from the mold.
- test button was evaluated for changes in degree of crosslinking or melt viscosity in a test employing a Rheometric Dynamic Spectrometer.
- the test which is useful in measuring the thermal stability of a sample, determines storage modulus of a sample as a function of time at a constant shear of 10 radians per second at 300° C.
- the cobalt salt-containing sample has a storage modulus value about 2.8 times greater than the control and the zinc salt-containing sample has a storage modulus value about 2.4 times greater than, the control. Since melt viscosity (degree of crosslinking) is directly proportional to storage modulus it is clear that the cobalt and zinc salts are acting as cure promoters for PPS as compared to the control in view of their substantially greater storage modulus values which accelerate throughout the length of the test.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/423,386 US4421910A (en) | 1982-09-24 | 1982-09-24 | Polymer stabilization |
| CA000433387A CA1223688A (en) | 1982-09-24 | 1983-07-27 | Polymer stabilization |
| AT83109200T ATE25696T1 (de) | 1982-09-24 | 1983-09-16 | Stabilisierung von polymeren. |
| DE8383109200T DE3370008D1 (en) | 1982-09-24 | 1983-09-16 | Polymer stabilization |
| EP83109200A EP0104562B1 (en) | 1982-09-24 | 1983-09-16 | Polymer stabilization |
| ES525724A ES8506333A1 (es) | 1982-09-24 | 1983-09-19 | Un metodo de aumentar la viscosidad de fusion de polimeros de poli(sulfuro de arileno) |
| JP58175145A JPS59131650A (ja) | 1982-09-24 | 1983-09-21 | 重合体組成物 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/423,386 US4421910A (en) | 1982-09-24 | 1982-09-24 | Polymer stabilization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4421910A true US4421910A (en) | 1983-12-20 |
Family
ID=23678723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/423,386 Expired - Fee Related US4421910A (en) | 1982-09-24 | 1982-09-24 | Polymer stabilization |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4421910A (en:Method) |
| EP (1) | EP0104562B1 (en:Method) |
| JP (1) | JPS59131650A (en:Method) |
| AT (1) | ATE25696T1 (en:Method) |
| CA (1) | CA1223688A (en:Method) |
| DE (1) | DE3370008D1 (en:Method) |
| ES (1) | ES8506333A1 (en:Method) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4826906A (en) * | 1987-06-22 | 1989-05-02 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketone) compositions improved in both melt stability and crystallinity |
| EP0345094A1 (en) | 1988-06-02 | 1989-12-06 | Toray Industries, Inc. | Polyphenylene sulfide composition |
| US20040192882A1 (en) * | 2003-03-24 | 2004-09-30 | Vidaurri Fernando C. | Method of measuring extent of curing of compacted poly (arylene sulfide) |
| US20090016787A1 (en) * | 2007-07-10 | 2009-01-15 | Konica Minolta Business Technologies., Ltd. | Transfer belt for electrophotography and image forming apparatus equipped therewith |
| WO2022080731A1 (ko) * | 2020-10-12 | 2022-04-21 | 주식회사 엘지화학 | 폴리아릴렌설파이드 수지 조성물, 및 폴리아릴렌설파이드 수지의 성형성을 향상시키는 방법 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1995366B1 (en) | 2007-05-21 | 2015-05-06 | Samsung Electronics Co., Ltd. | Washing machine and control method of maintaining a balanced state of laundry thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293208A (en) * | 1963-07-03 | 1966-12-20 | American Cyanamid Co | Stabilization of polyolefins with certain metal dithiophosphinate salts |
| US3325444A (en) * | 1964-07-10 | 1967-06-13 | American Cyanamid Co | Stabilized methyl methacrylate monomer and polymer compositions containing a dithio phosphinic acid or a metal salt thereof |
| US3658753A (en) * | 1970-07-01 | 1972-04-25 | Phillips Petroleum Co | Color stabilized poly(arylene sulfide) resins |
| US3755396A (en) * | 1971-10-01 | 1973-08-28 | American Cyanamid Co | Cobalt dicyclohexyldithiophosphinate and stabilization of polyolefinstherewith |
| US3812080A (en) * | 1973-05-11 | 1974-05-21 | American Cyanamid Co | Nickel and cobalt dicyclohexyldithio-phosphinates as flame-retardants for styrene polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3409654A (en) * | 1963-07-03 | 1968-11-05 | American Cyanamid Co | Copper and zinc salts of dicyclohexyl phosphinic acid |
| US3801539A (en) * | 1971-10-01 | 1974-04-02 | American Cyanamid Co | Cobalt dicyclohexyldithiophosphinate stabilization of polyolefins |
| US3883460A (en) * | 1973-04-16 | 1975-05-13 | Firestone Tire & Rubber Co | Stabilization of polybutadiene resin |
-
1982
- 1982-09-24 US US06/423,386 patent/US4421910A/en not_active Expired - Fee Related
-
1983
- 1983-07-27 CA CA000433387A patent/CA1223688A/en not_active Expired
- 1983-09-16 DE DE8383109200T patent/DE3370008D1/de not_active Expired
- 1983-09-16 EP EP83109200A patent/EP0104562B1/en not_active Expired
- 1983-09-16 AT AT83109200T patent/ATE25696T1/de active
- 1983-09-19 ES ES525724A patent/ES8506333A1/es not_active Expired
- 1983-09-21 JP JP58175145A patent/JPS59131650A/ja active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293208A (en) * | 1963-07-03 | 1966-12-20 | American Cyanamid Co | Stabilization of polyolefins with certain metal dithiophosphinate salts |
| US3325444A (en) * | 1964-07-10 | 1967-06-13 | American Cyanamid Co | Stabilized methyl methacrylate monomer and polymer compositions containing a dithio phosphinic acid or a metal salt thereof |
| US3658753A (en) * | 1970-07-01 | 1972-04-25 | Phillips Petroleum Co | Color stabilized poly(arylene sulfide) resins |
| US3755396A (en) * | 1971-10-01 | 1973-08-28 | American Cyanamid Co | Cobalt dicyclohexyldithiophosphinate and stabilization of polyolefinstherewith |
| US3812080A (en) * | 1973-05-11 | 1974-05-21 | American Cyanamid Co | Nickel and cobalt dicyclohexyldithio-phosphinates as flame-retardants for styrene polymers |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4826906A (en) * | 1987-06-22 | 1989-05-02 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketone) compositions improved in both melt stability and crystallinity |
| EP0345094A1 (en) | 1988-06-02 | 1989-12-06 | Toray Industries, Inc. | Polyphenylene sulfide composition |
| US20040192882A1 (en) * | 2003-03-24 | 2004-09-30 | Vidaurri Fernando C. | Method of measuring extent of curing of compacted poly (arylene sulfide) |
| US6946540B2 (en) | 2003-03-24 | 2005-09-20 | Chevron Phillips Chemical Company, Lp | Method of measuring extent of curing of compacted poly(arylene sulfide) |
| US20090016787A1 (en) * | 2007-07-10 | 2009-01-15 | Konica Minolta Business Technologies., Ltd. | Transfer belt for electrophotography and image forming apparatus equipped therewith |
| US8103202B2 (en) | 2007-07-10 | 2012-01-24 | Konica Minolta Business Technologies, Inc. | Transfer belt for electrophotography and image forming apparatus equipped therewith |
| WO2022080731A1 (ko) * | 2020-10-12 | 2022-04-21 | 주식회사 엘지화학 | 폴리아릴렌설파이드 수지 조성물, 및 폴리아릴렌설파이드 수지의 성형성을 향상시키는 방법 |
| CN116057121A (zh) * | 2020-10-12 | 2023-05-02 | 株式会社Lg化学 | 聚亚芳基硫醚树脂组合物以及改善聚亚芳基硫醚树脂的成型性的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59131650A (ja) | 1984-07-28 |
| ES525724A0 (es) | 1985-07-01 |
| DE3370008D1 (en) | 1987-04-09 |
| EP0104562A1 (en) | 1984-04-04 |
| EP0104562B1 (en) | 1987-03-04 |
| ATE25696T1 (de) | 1987-03-15 |
| JPH0124416B2 (en:Method) | 1989-05-11 |
| CA1223688A (en) | 1987-06-30 |
| ES8506333A1 (es) | 1985-07-01 |
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